Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
  • C09B67/0035—Mixtures of phthalocyanines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
  • C09B62/26—Porphyrins; Porphyrazins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
  • C09B67/0042—Mixtures containing two reactive dyes one of them being an azo dye

Definitions

• the invention relates to mixtures of phthalocyanine reactive dyestuffs which, when used for dyeing cellulose fibers or regenerated cellulose fibers, have an improved appearance of the goods compared with the individual components and improved combination properties with reactive yellow dyestuffs when used for producing green dyeings, and to novel dyestuffs.
• phthalocyanine reactive dyestuffs are used by the padding process for producing turquoise dyeings or brilliant green dyeings on fiber materials of natural or regenerated cellulose fiber substrates or on mixtures of such fiber materials with synthetic fiber materials of polyester or polyamide, an appearance of the goods is obtained which shows a restriction in levelness which depends greatly on the fiber material and on the illumination conditions, compared with the levelness of a blue, yellow or red dyeing produced in accordance with the prior art and combination dyeings thereof to give customary fashionable shades.
• This restriction in levelness typical of phthalocyanine reactive dyestuff is based on the different fixing properties of a phthalocyanine dyestuff on the natural and regenerated cellulose fibers.
• the breaking up of a turquoise-green mixture when used for dyeing by the padding process is known both for cotton and for regenerated cellulose fibers.
• the dyeings obtainable when dyeing with copper phthalocyanine dyestuffs in combination with yellow azo dyestuffs show the problem of fiber unlevelness (skitteriness) and of tailing (shift in shade due to preferential uptake of turquoise from the padding trough).
• the phthalocyanine dyestuff is preferentially taken up from the chassis.
• the material is subsequently wound onto large rolls, so that the portion padded first is stored inside the wound goods.
• the outer layer is first fed to the continuous washing unit. The inner portion of the wound goods is therefore stored for longer.
• the invention is based on the object of providing phthalocyanine reactive dyestuff mixtures for producing turquoise and green dyeings which, with a good fixing yield under dyeing conditions appropriate in practice, produce an improved appearance of the goods compared with the individual dyestuffs, and are suitable in particular for the reactive pad dyeing process, in which the residual and rinsing liquors should be free from AOX.
• the dyestuff mixture should have a high solubility and insensitivity to electrolytes and show dyeing properties which are constant in shade in the course of time, level over the surface and reproducible under variable temperature, alkali and liquor conditions.
• the present invention relates to a dyestuff mixture of at least two phthalocyanine reactive dyestuffs which contain a different reactive group, which comprises at least one chlorine-free phthalocyanine-fluoropyrimidinyl reactive dyestuff 2 and at least one phthalocyanine-vinylsulfonyl reactive dyestuff 1 and/or one phthalocyanine-monochlorotriazinyl reactive dyestuff 3.
• the invention furthermore relates to a padding process using a mixture of phthalocyanine reactive turquoise blue dyestuffs in combination with a mixture of yellow reactive dyestuffs for dyeing cellulose fibers or regenerative cellulose fibers which shows an improved appearance of the goods compared with the use of the individual components.
• the invention furthermore relates to novel phthalocyanine-fluoropyrimidinyl reactive dyestuffs 2. These are particularly suitable for the mixture according to the invention.
• x 1 to 3, in particular 1.5 to 2,
• y 1 to 3, in particular 1 to 2, especially 1.3 to 1.8, and
• the radical --SO 2 --CH 2 --CH 2 --OSO 3 H is in the p-position.
• B an optionally substituted arylene, aralkylene or optionally substituted alkylene bridge or a direct bond
• R 1 , R 2 , R 3 , R 4 independently of one another hydrogen or an optionally substituted alkyl or aryl radical
• w+v+z 3.0 to 4.0.
• Y O, S or NR 1 .
• Preferred alkyl radicals R 1 to R 4 are C 1 -C 4 -alkyl or C 1 -C 4 -alkyl radicals which are substituted by OH, SO 3 H, OSO 3 H or CO 2 H.
• Preferred aryl radicals R 1 to R 4 are phenyl and phenyl radicals which are substituted by OH, SO 3 H or CO 2 H.
• the mixture additionally comprises a reactive dyestuff yellow mixture of the dyestuffs 4, 5 or 6 and the dyestuff 7, 8 or 9 of the structures shown below: ##STR9##
• the levelness of the appearance of the goods of phthalocyanine reactive pad dyeings on cellulose fibers can be improved by mixtures of different phthalocyanine reactive dyestuffs, in particular by mixtures of phthalocyanine reactive dyestuffs which contain different reactive groups. It has furthermore been found that the levelness of brilliant green dyeings based on phthalocyanine and brilliant azo yellow reactive dyestuffs can be improved if mixtures of two reactive yellow dyestuffs which likewise contain different reactive groups are used as the yellow content.
• the process according to the invention is advantageously suitable for producing brilliant green shades by combined use of a mixture of the dyestuffs 1 and 2 or 2 and 3 with a mixture of the dyestuffs 4, 5 or 6 independently of one another with the dyestuffs 7, 8 or 9.
• Particularly preferred reactive turquoise blue mixtures are:
• Particularly preferred additional reactive yellow mixtures are:
• Mixture 12 dyestuffs 5 and 9
• the mixtures comprise, based on the total dyestuff content:
• Dyestuffs 1 0 to 70, in particular 40 to 55% by weight
• Dyestuffs 2 30 to 70, in particular 45 to 60% by weight
• Dyestuff 3 0 to 70, in particular 0 to 45% by weight
• Dyestuff 4 30 to 70, in particular 50% by weight
• Dyestuff 5 30 to 70, in particular 50% by weight
• Dyestuff 6 30 to 70, in particular 50% by weight
• Dyestuff 7 30 to 70, in particular 50% by weight
• Dyestuff 8 30 to 70, in particular 50% by weight
• Dyestuff 9 30 to 70, in particular 50% by weight
• the dyestuff mixtures according to the invention comprise up to 50 parts of an inorganic salt, such as, for example, sodium chloride or sodium sulfate, per 100 parts of dyestuff.
• the mixtures according to the invention furthermore preferably comprise a buffer, in particular an inorganic buffer, which produces a buffering range between pH 6.5 to 7.5.
• the mixtures according to the invention preferably comprise dispersing agents, in particular 0.5 to 10 parts by weight of an organic, anionic dispersing agent, based on the total mixture, and a dust removal agent, preferably 0.5 to 5 parts by weight, based on the total mixture.
• the dyestuff mixture can preferably be used for dyeing cotton and other cellulose fibers in the cold pad-batch process.
• Suitable materials are both pure cellulose fiber materials and mixtures thereof with polyester, such as polyester/cotton, polyester/viscose and polyester/linen, and mixtures of various cellulose fibers, such as cotton/viscose staple or cotton/linen.
• the main field of use of the mixture is dyeing of cotton woven and knitted goods and of terry goods.
• Batching temperatures of 20° C. to 30° C. are possible, the preferred batching temperature is 25° C., and the preferred batching temperature is identical to the preferred padding temperature.
• the short batching time with respect to the depth of color for turquoise and green dyeings is to be emphasized as a technical advance.
• the mixture is used in the pad steam process.
• mixtures according to the invention are particularly suitable for dyeing by the pad process, preferably in accordance with the following standard recipes:
• mixtures according to the invention are furthermore particularly suitable for dyeing in the exhaustion process, preferably in accordance with one of the following schemes:
• the dyestuff mixture can preferably be used for dyeing cotton and other cellulose fibers in the exhaustion process on customary dyeing units.
• Dyeing temperatures of 60° C. to 95° C. are possible, the preferred dyeing temperature is 80° C. and the preferred start temperature is 60° C.
• B an optionally substituted arylene, aralkylene or optionally substituted alkylene bridge or a direct bond
• R 1 , R 2 , R 3 , R 4 independently of one another hydrogen or an optionally substituted alkyl or aryl radical
• w a number from 0 to 3
• z' a number from 0.5 to 2.0
• v a number from 0.5 to 2.5
• R 5 is H, CO 2 H, SO 3 H, CH 3 or OCH 3 .
• Particularly preferred phthalocyanine reactive dyestuffs 2b are those of the formulae 2.1, 2.2 and 2.3.
• the temperature of the liquor is 25° C.
• the web of fabric impregnated with the dye liquor is wound up, packed in polyethylene film and batched for 24 hours under slow rotation. It is then washed out on an eight-box continuous open-width washing machine in accordance with the following plan. Rinse cold twice, rinse warm twice, extract at the boil twice, rinse warm, rinse cold.
• the temperature of the liquor is 25° C.
• the web of fabric impregnated with the liquor is wound up, packed in polyethylene film and batched for 48 hours under slow rotation. It is then washed out on an eight-box continuous open-width washing machine in accordance with the following plan: Rinse cold twice, rinse warm twice, extract at the boil twice, rinse warm, rinse cold.
• a deep green dyeing which is level over the surface and the same at the ends and has good fastness properties is obtained.
• the temperature of the padding liquor is 25° C.
• the web of fabric impregnated with the dye liquor is wound up, packed in polyethylene film and batched for 48 hours under slow rotation. It is then washed out on an eight-box continuous open-width washing machine in accordance with the following plan: Rinse cold twice, rinse warm twice, extract at the boil twice, rinse warm, rinse cold.
• a deep green dyeing which is level over the surface and the same at the ends and has good fastness properties is obtained.
• the temperature of the liquor is 30° C.
• the web of goods then passes through a chemical pad.
• the aqueous chemical padding bath comprises, in 1000 parts, 250 parts of sodium chloride and 20 parts of sodium hydroxide solution of specific gravity 1.5.
• the web of goods is transferred to a high-speed steamer and steamed at 106° C. for 60 seconds. Thereafter, it is washed out on an eight-box washing machine in accordance with the plan described:
• a phthalocyanine reactive dyestuff mixture 100 parts of bleached cotton knitted goods and 3 parts of a phthalocyanine reactive dyestuff mixture are added to 1000 parts of an aqueous dye liquor on a winch vat at 60° C.
• the appearance of the goods of the resulting dyeing is more level than the appearance of the goods of a dyeing obtained in accordance with the same dyeing plan, in which in each case 3 parts of only dyestuff 1 or dyestuff2 were employed.
• the liquor After treatment at this temperature for 10 minutes, the liquor is heated to 60° C. in the course of 15 minutes, and 100 parts of a dyestuff solution comprising 1 part of a mixture of
• the liquor is drained off and the goods are rinsed twice at 60° C. and twice at 80° C. They are then soaped at the boil for 15 minutes and the wash liquor is drained off After rinsing cold, a level green dyeing with good fastness properties is obtained.
• the appearance of the goods is more level than the appearance of the goods of a dyeing obtained in accordance with the same dyeing plan in which in each case instead of the ,mixture of dyestuff 1 and 2, 1 part of the dyestuff 1 or 1 part of the dyestuff 2 was employed.
• 100 parts of a bleached cotton yarn are treated on a commercially available yarn dyeing apparatus at a liquor circulation of 27 1/kg/minute with 750 parts of a dye liquor, heated to 60° C., which comprises
• the bath is heated to 80° C. in the course of 20 minutes and kept at this temperature for 60 minutes. After this period, the liquor is drained off and the goods are rinsed twice with 750 parts of a liquor heated to 60° C. Thereafter, the bath is topped up with 750 parts of a fresh liquor heated to 60° C., 0.5 parts of a 60% strength acetic acid is added and the liquor is heated to 80° C. After treatment at this temperature for 10 minutes, the liquor is drained off, the bath is topped up to the same volume with fresh liquor of 60° C. and the liquor is brought to 95° C. After treatment at this temperature for 15 minutes, the liquor is drained off and the goods are rinsed cold with an overflow.
• a level deep green dyeing is obtained.
• the bath is heated to 80° C. in the course of 20 minutes and kept at this temperature for 60 minutes. After this period, the liquor is drained off and the goods are rinsed twice for 10 minutes each time with 800 parts of a liquor heated to 60° C. and twice with 800 parts of a liquor heated to 80° C.
• the goods are then heated to 95° C. with fresh liquor and extracted at the boil for minutes. After the wash liquor has been drained off, the goods are rinsed cold.
• the bath is heated to 80° C. in the course of 20 minutes and kept at this temperature for 60 minutes. After this period, the liquor is drained off and the goods are rinsed twice for 10 minutes each time with 800 parts of a liquor heated to 60° C. and twice with 800 parts of a liquor heated to 80° C.
• the goods are then heated to 95° C. with fresh liquor and extracted at the boil for 20 minutes. After the wash liquor has been drained off, the goods are rinsed cold.
• the material on the suction filter is stirred with 1000 parts of ice-water.
• the pH is brought to 6.0 to 6.5 with dilute sodium hydroxide solution at 0° to 5° C. and is kept at this value for 3 hours.
• the pH is then increased to 9.5 to 10.0 and, after a subsequent stirring time of two hours, the temperature is allowed to rise to 20° to 25° C. After the mixture has been stirred at 20° to 25° C. for 10 hours, the pH is brought to 7 with dilute hydrochloric acid and the dyestuff is salted out with sodium chloride.
• the dyestuff is filtered off with suction and dried at 60° C. in vacuo.
• the dyestuff essentially corresponds, in the form of its free acid, to the formula ##STR16## and dyes cotton in clear turquoise blue shades and gives a turquoise blue print on cotton.
• the degree of sulfonation and the content of sulfonamide groups in the dyestuffs of Examples 10 and 11 can be controlled in a known manner by slight variation of the sulfochlorination conditions.
• a turquoise dyestuff for reactive printing which is particularly readily water-soluble and has the formula ##STR18## is obtained if the amount of acylated 1,3-diaminobenzene and ammonium chloride in Example 10 are reduced by about 10%.
• the reactive dyestuffs of Examples 10 to 12 can also be prepared by reacting 0.1 mol of a dyestuff intermediate product of the formula ##STR20## with 0.08-0.15 mol of 2,4,6-trifluoropyrimidine in 250 ml of water at 40°-50° C. During this reaction, the pH is kept constant at 6.5 by addition of sodium carbonate solution. After about 3 hours, the condensation reaction has ended. The resulting dyestuff is salted out with potassium chloride, isolated by filtration with suction and dried.
• the dyestuff intermediate product employed, the color base outlined above, is obtained by condensation of copper phthalocyanine-sulfonyl chloride with 3-aminoacetanilide and, if appropriate, ammonium chloride and subsequent hydrolysis of the N-acyl grouping.
• the material on the suction filter is stirred into 1000 parts of ice-water. 26.5 parts of a mixture of 2,4-difluoro-6-(3-aminophenyl)aminopyrimidine (content about and 4,6-difluoro-2-(3-aminophenyl)aminopyrimidine (content about 20%) (for the preparation, see Example 10) are stirred in.
• the pH of the suspension is brought to 9.0 in the course of 90 minutes by addition of sodium hydroxide solution, the temperature being increased to 23° C. at the same time.
• the mixture is stirred at pH 9 and 20° to 24° C. until the reaction has ended.
• the dyestuff is salted out, subsequently stirred briefly at pH 7, filtered off with suction and covered several times with dilute NaCl solution.
• the dyestuff is dried at 60° C. As the free acid, it corresponds to the formula ##STR24##
• the dyestuff dyes cotton in bluish-tinged green shades which are extremely fast to washing and light, the optimum dyeing temperature being 80° C.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=7761784

Family Applications (1)

Country Status (3)

Cited By (9)

Citations (10)

Family Cites Families (6)

• 1995
  • 1995-05-12 DE DE19517503A patent/DE19517503A1/de not_active Withdrawn
• 1996
  • 1996-04-30 EP EP96106797A patent/EP0742270B1/de not_active Expired - Lifetime
  • 1996-05-07 US US08/646,185 patent/US5709717A/en not_active Expired - Fee Related

Patent Citations (10)

Also Published As

Similar Documents

Legal Events